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Oxidative C-H Bond Activation:Study on DDQ-Induced Intramolecular Cyclization Reactions and Application to the Formal Synthesis of Neopeltolide

Tu, Wangyang (2010) Oxidative C-H Bond Activation:Study on DDQ-Induced Intramolecular Cyclization Reactions and Application to the Formal Synthesis of Neopeltolide. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) has been found to be an excellent reagent for oxidatively activating benzylic C-H bonds, and the in-situ generated oxocarbenium ions can be captured by nucleophiles appended in the molecules. A variety of aromatic methyl ethers with different substituents are shown to be reactive with DDQ, and common protecting groups are well tolerated. The enol acetate group is the most reliable and productive nucleophile compared with other candidates and provides the 2,6-disubstituted tetrahydropyrone product as exclusively the cis isomer. This method has been successfully applied to the macrocyclic systems. The valuable macrocyclic oxocarbenium ions are readily formed when treating the substrates with DDQ. The reactions are generally slower than those of acyclic substrates but the yields are almost unaffected. The ring size has no influence on the diastereoselectivity of cyclization.A convergent formal synthesis of natural product neopeltolide was accomplished from three building blocks by utilizing the DDQ mediated cyclization reaction as the key transformation. A novel intramolecular hydrosilylation-Tamao oxidation reaction is employed to synthesize the precursor for the key step. This approach to the natural product has minimized the involvement of protecting groups and conveniently provided an opportunity to access the natural product analogues through double bond functionalizations.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Tu, Wangyangwat6@pitt.eduWAT6
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairFloreancig, Paulflorean@pitt.eduFLOREAN
Committee MemberDay, Billybday@pitt.eduBDAY
Committee MemberWilcox, Craigdaylite@pitt.eduDAYLITE
Committee MemberCurran, Denniscurran@pitt.eduCURRAN
Date: 29 January 2010
Date Type: Completion
Defense Date: 9 September 2009
Approval Date: 29 January 2010
Submission Date: 28 September 2009
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: cyclization; DDQ; macrocyclic; C-H bond activation; neopeltolide
Other ID:, etd-09282009-132254
Date Deposited: 10 Nov 2011 20:02
Last Modified: 15 Nov 2016 13:50


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